Alkylamino-2-hydroxypropyl quaternary ammonium compounds



United States Patent 3,271,443 ALKYLAMINO-Z-HYDROXYPROPYL QUATER- NARY AMMONIUM CONLPOUNDS Donald M. Burness, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Feb. 18, 1964, Ser. No. 345,579 4 Claims. (Cl. 260-501) This application is a continuation-in-part of application Serial No. 137,035, filed September 11, 1961, and now US. Patent No. 3,189,457.

This invention relates to certain quaternary ammonium salts which are useful sensitizers for silver halide emulsions.

Various types of compounds have been suggested as sensitizers for use in silver halide emulsions but because of some characteristic many of these leave something to be desired. For instance, a difliculty encountered with several sensitizers is that they appear to diffuse to a greater or lesser extent therefrom with the result that their effect upon the photographic properties of the emulsion may be decreased upon storage.

One object of my invention is to provide quaternary ammonium compounds which diffuse, if at all, only to a small extent from the photographic emulsion in which they have been incorporated. Other objects of my invention will appear herein.

I have found certain novel quaternary ammonium salts useful as addenda to photographic emulsions which compounds can be represented by the general formula:

where Y is an alkylthio group of 6-30 carbon atoms or a secondary or a tertiary amino group containing a linear chain of 10-30 carbon atoms, R represents lower alkyl groups of 14 carbon atoms, and X is a suitable anion, or, where a his compound such as a dimercaptan or diamine is used in their preparation, by the formula:

wherein Z is alkylenedithio or alkylenediamino, the chain connecting the end S or N atoms being either 'a straight aliphatic carbon chain or an aliphatic hetero chain, but in either case having at least 4 carbon atoms.

The preparation of compounds in accordance with my invention is conveniently carried out in excellent yield by reacting a quaternary ammonium epoxide with an appropriate amine or mercaptan. Some amines which are useful in preparing compounds in accordance with my invention are those having the formulas C H NH C H NH and C12H25NH2. substituted amines such as C H NHCH may also be employed. Some mercaptans which are useful for reacting with a quaternary ammonium epoxide to give compounds in accordance with my invention are C H SH, C H SH, C H SH and C H SH. Amines or mercaptans having greater numbers of carbon atoms may be used if the resulting compounds show useful properties for sensitizing photographic emulsions.

In the preparation of his compounds in accordance with my invention the following dimercapto compounds are suitable for reacting with quaternary ammonium epoxides to prepare quaternary ammonium compounds in accordance with the invention:

HS CH CONH (CH NHCO (CH SH (HSCH CH 8 HS CH SH and the like.

"ice

Examples of diamino compounds suitable for reacting with quaternary ammonium epoxides to prepare compounds in accordance with the invention are:

and the like.

Some of the quaternary ammonium epoxides which may be reacted with amines or mercaptans to form compounds in accordance with my invention are: 2,3-epoxypropyltr-imethylammoniurn p-toluenesulfonate, 2,3-epoxypropyldimethylpropylammonium p-toluenesulfonate, 2,3- epoxypropyldiethylmethylammonium p-toluenesulfonate, and 2,3-epoxypropyltrimethylammonium chloride.

The preparation of compounds of the mono-quaternary type in accordance with my invention is conveniently carried out in excellent yield by the reaction of a quaternary ammonium epoxide with an amine or mercaptan in accordance with the following equations:

RI CH2CHOHOHz1:IR3-X R being alkyl groups of 1-4 carbon atoms, R being alkyl groups of C C (mercaptan) or C -C (amine), R" being either hydrogen or alkyl of l-4 carbon atoms and X being any suitable anion such as p-toluenesulfonate, perchlorate, chloride, bromide, sulfate, phosphate, methosulfate or the like.

For the preparation of compounds in accordance with my invention of the bisquaternary ammonium type the dimercaptan or diamine is reacted with the quaternary ammonium epoxide to result in a compound having the formula:

where R is alkyl of 1-4 carbon atoms, X- is a suitable anion such as listed above and Z is alkylenedithio or alkylenediamino, the chain connecting the end S or N atoms containing at least 4 carbon atoms with or without hetero atoms such as sulfur, nitrogen or oxygen. For instance, if the nitrogens are joined by a hetero chain it should be an alkylene chain of at least 4 and not more than about 12 carbon atoms which is interrupted by at least one -O, S, or

group.

The following example illustrates the preparation of a compound in accordance with my invention:

Example grams of 3-dimethylamino-l,Z-epoxypropane prepared by the method described by Gilman and Fullhart, JACS, 71, 1430 (1949), in solution in 600 m1. of dry benzene was mixed with grams of methyl p-toluenesulfonate over a 10-minute period at 3035 C. The mixture was allowed to stand at 25 C. overnight whereupon it was filtered and recrystallized from acetone to give 189 grams of colorless plate-formed crystals. 11.5 grams of the 2,3-epoxypropyltrimethylammonium p-toluenesulfonate thus prepared was dissolved in 25 ml. of methanol which was added to a solution consisting of 14.8 grams of dodecylamine (reactant YH) in 25 ml. of methanol. While the addition was taking place over a half-hour period, the mass was stirred and heated at 45 C. It was then maintained at this temperature with AMMONIUM p-TOSYLATE WITH AMINES AND MER- CAPTANS Reactant YH Percent M.P., 0. Formula Yield CmHzlNHz 77 113-130 C23HMN204S 73 106-167 O25H4EN204S 66 111-181 C27H52N2O4S 72 100-124 C2aH54N20-1S 87 120-121 Cl9H35NO4s2 88 87-91 czlHaoNoisz 79 94-120 C23H43N0 Sz 74: 89-155 C25H 7NO S2 CrsHaaSH 88 78-190 CzgHaaNOqSz The preparation of biscompounds in accordance with my invention is carried out by the same procedure as specified in the example except that dimercapto or diamino compounds are reacted with the quaternary ammonium epoxides, the latter in an amount of substantially 2 equivalents thereof per unit of dimercapto or diamino compound, thereby forming a compound having the formula:

wherein each R is an alkyl of 1-4 carbon atoms, X- is a suitable anion corresponding to that supplied by the quaternary ammonium epoXide compound and Z is alkyl enedithio or alkylenediamino the chain connecting the S or N atoms containing at least 4 carbon atoms, depending upon whether a dimercapto or diamino reactant was employed.

The compounds described may be used in various kinds of silver halide photographic emulsions such as X-ray or other non-optically sensitized emulsions or in orthochromatic, panchromatic or infrared sensitive emulsions. Various silver salts may be used as a light sensitive salt in the emulsion such as silver bromide, silver iodide, silver chloride, or mixed silver halides. The sensitizer may be used in emulsions intended for color photography such as emulsions containing color forming couplers or emulsions to be developed by solutions containing colorgenerating materials, all as is more extensively described in my parent application Serial No. 137,035, of which this is a continuation-in-part;

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it Will be understood that variations and modifications can be effected Within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.

I claim:

1. A compound selected from the group consisting of the compounds having the formula wherein R is a linear hydrocarbon radical of 10-30 carbon atoms; R" is hydrogen or a lower alkyl of 1-4 carbon atoms; R is lower alkyl of 1-4 carbon atoms; and X" is an anion; and the compounds having the formula wherein R is lower alkyl of 1-4 carbon atoms; X is an anion; and Z is a diamino group in whichthe amino groups are joined by an alkylene chain of at least 4 and not more than about 12 carbon atoms or an alkylene of at least 4 and not more than about 12 carbon atoms which is interrupted by at least one O-, --S, or

group.

2. A compound having the formula:

wherein R is alkyl of 1-4 carbon atoms and X is an anion.

3. A compound having the formula:

wherein R is alkyl of 1-4 carbon atoms and X- is an anion.

4. 3 n-dodecylamino-2-hydroxypropyltrimethylammonium p-toluenesulfonate.

References Cited by the Examiner UNITED STATES PATENTS 2,454,547 11/1948 Bock et al 260-5676 2,548,679 4/1951 Olin 260567.6 2,689,790 9/1954 Mowry et a1. 260567.6 X 2,714,119 7/1955 Grounse 260-561 2,777,858 l/l957 Girod et a1 260-567.6 X

CHARLES B. PARKER, Primary Examiner.

F D. HIGEL, Assistant Examiner. 

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE COMPOUNDS HAVING THE FORMULA 